Ferritic-austenitic stainless steel

ABSTRACT

An austenitic-ferritic stainless steel consisting essentially of up to about 0.06 percent carbon, about 4.0 to less than 11.0 percent manganese, about 19 to about 24 percent chromium, about 0.12 to about 0.26 percent nitrogen, nickel up to about 3.0 percent, and remainder substantially iron except for incidental impurities. The austenite-ferrite balance, ranging between 10 percent and 50 percent austenite, is stable, and the steel exhibits high toughness, corrosion resistance and excellent weldability.

United States Patent Espy 1 [54] FERRITIC-AUSTENITIC STAINLESS STEEL [75] Inventor: Ronald H. Espy, Randallstown, Md. [73] Assignee: Armco Steel Corporation,

- Middletown, Ohio [22] Filed: Dec. 23, 1970 [21] Appl. No.: 101,096

[52] U.S. Cl ..75/l26 B, 75/126 J, 75/128 A,

. 7 148/39 [51] Int. Cl ..C22c 39/14 [58] Field or Search ..75/126 J, 126 B, 75/128 N [56. 1 References Cited UNITED STATES PATENTS 2,198,598 4/1940 Becket ....75/l261 51 May 29, 1973 6/1965 Kanter .l ..7S/128N 10/1964 'Lula ..75/128N Primary Examiner-l-lyland Bizot Attorney-Melville, Strasser, Foster & Hoffman 57 ABSTRACT An austenitic-ferritic stainless steel consisting essentially of up to about 0.06 percent carbon, about 4.0 to

less than 11.0 percent manganese, about 19 to about 12 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a modified chromium stainless steel (low'in nickel, copper and cobalt) of stable ferritic-austenitic structure having excellent toughness, ductility, corrosion resistance and welding characteristics. The alloy of the invention, by reason of its compositional balance, achieves a structure of from percent to 50 percent austenite (preferably percent to 30 percent) in a ferritic matrix which resists transformation into martensite despite cold working, heat treatment, or welding.

The stainless steel of this invention has particular utility as weldments in straight chromium steels, for fabrication into fasteners which require cold heading, and a variety of other applications requiring relatively high strength and ductility, good weldability, and high resistance to intergranular corrosion in strongly oxidizing media, as well as good resistance to stress corrosion in chloride media.

2. Description of the Prior Art Among the numerous alloys developed to offset the scarcity and high cost of nickel are those disclosed in US Pat. No. 2,778,731 issued Jan. 22, 1957, to D.

Carney, consisting of 0.06 percent to 0.15 percent car'- bon, 14 percent to 20 percent manganese, 17 percent to 18.5 percent chromium, 0.05 percent to 1.0 percent nickel, 0.25 percent to 1.0 percent silicon, 0.25 percent to 1.0 percent nitrogen, and remainder iron; B '& W CROLOY 299 consisting of 0.20 percent carbon, 15.0 percent manganese, 17.0 percent chromium, 1.5 percent nickel, 0.35 percent nitrogen, and remainder iron; and other fully austenitic steels such as Armco 16-16-1 and Allegheny Ludlum 205.

A fully austenitic stainless. steel having excellent physical properties and stress corrosion resistance at cryogenic temperatures, coupled with great tensile strength when drastically cold reduced, is described in copending application Ser. No. 868,893 filed Oct. 23, 1969, in the name of George N. Goller and Ronald H. Espy. This steel is non-magnetic.

Straight chromium stainless steels such as A.l.S.I. Types 430, 442 and 446 have the serious disadvantages of being brittle and subject to corrosion in the heat affected zone of the base metal of a weldment. Further, the unaffected base metal may be low in impact strength at room temperature.

Typical of austenitic stainless steels which transform with cold working to less ductile martensite is A.l.S.I. Type 304, consisting of 0.08 percent maximum carbon, 2.0 percent maximum manganese, 18 percent to 20 percent chromium, 8 percent to 10.50 percent nickel and balance iron.

An alloy developed for cold heading applications which does not transform to martensite is designated as IN 744X. This steel contains about 26 percent chromium and is about half austenitic and half ferritic. Due to the high alloy content the cost is excessivelyhigh.

SUMMARY OF THE INVENTION The principal object of this invention is to provide a magnetic austenitic-ferritic stainless steel essentially consisting of'chromium, manganese, carbon and nitrogen which is stable against transformation to martensite regardless of cold working, heat treatment or welding,

which has good ductility, toughness and corrosion resistance in its as-welded condition, and high strength,

but which nevertheless is relatively low in cost because of lower alloy content than prior art alloys offered for applications requiring the above properties.

According to the invention a stainless steel having a two-phase structure comprising between 10 percent and 50 percent austenite in a ferrite matrix consists essentially of from about 4.0 percent to less than 11.0 percent manganese, about 19 percent to about 24 percent chromium, and about 0.12 percent to about 0.26 percent nitrogen. Carbon is of course present and is limited to a maximum of about 0.06 percent. Phosphorus and sulfur, normally present as impurities, are limited to a maximum of about 0.03 percent each. Silicon is also normally present, in amounts up to 1.0 percent maximum. Nickel may be present, ranging from trace amounts up to about 3.0 percent. Copper and cobalt, if present as residual elements, are limited to a maximum of about 0.5 percent each. The balance is of course iron, together with incidental impurities.

Molybdenum may be substituted for chromium on a 1:1 basis in amounts up to about 5 percent for improved resistance to corrosion in pitting media.

Columbium may be added in amounts up to about 1 percent for improved weld area corrosion resistance.

The austenite level, preferably 20 percent to 30 percent, is achieved through addition of nitrogen (a strong austenite former) within the range of 0.12 percent and 0.26 percent. Carbon, although maintained at a low level, also contributes to some extent to austenite formation. The austenite is maintained at a stable level by reason of the chromium, manganese and nitrogen relationship. It is thus apparent that the compositional balance among the essential elements is in every sense critical. Unlike prior art austeniticferritic alloys, the nickel, copper and cobalt contents are maintained at low levels, and hence the steel of the invention is not subject to stress corrosion failure when exposed to hot chloride media. The use of manganese to stabilize the austenite balance results in a ductile material which is also resistant to stress cracking in hot chloride media. The low carbon content tends to prevent intergranular corrosion when welded.

At least about 0.12 percent nitrogen is necessary in order to form sufficient austenite. Nitrogen in excess of about 0.26 percent would exceed the solubility limit of this element and hence would result in porosity and unsoundness in the metal.

A minimum of about 4 percent manganese is required in order to balance the chromium and thereby stabilize the austenite. Excessive manganese adversely affects the balance with chromium, increasing the austenite level above the desired range, and the maximum manganese content is thus less-than 11.0 percent.

Nickel, if present, is limited to a maximum of about 3.0 percent. It has been found that the stress corrosion resistance of the metal will be adversely affected if the nickel content exceeds 3.0 percent. Within the prescribed range, nickel will of course increase the austenite level and thus cooperates with the nitrogen in this function, without adversely affecting toughness.

PREFERRED EMBODIMENTS OF THE INVENTION While, as indicated above, in its broad ranges the steel of the invention consists essentially of carbon up to about 0.06 percent, manganese about 4.0 percent to less than I 1.0 percent, chromium about l9 percent to about 24 percent, nitrogen about 0.12 percent to about 0.26 percent, nickel up to about 3.0 percent, phosphorus and sulfur up to about 0.03 percent each, silicon up to about 1.0 percent, copper and cobalt up to about 0.5 percent each, and remainder substantially iron, a preferred composition comprises about 0.02 percent carbon, about 6.0 percent manganese, phosphorus and sulfur low, about 0.40 percent silicon, about 2l.O percent chromium, about 0.20 percent nickel, about 0.20 percent nitrogen, copper and cobalt low, and balance substantially iron.

A series of heats was prepared in order to establish parameters for the composition which would achieve the novel combination of properties. The compositions of these heats are setforth in Table l below. Heats designated as B, E, H, I, J, K, L, P and Q are steels of the invention TABLE 1 Heat 0. Mn P S Si Cr Ni N A 0. 75 Low 0. 015 0. 50 26. 00 0. 25 0. 20 B 5. 85 0. 017 0. 023 0. 41 21. 12 0. 14 0. 23 C. 6. 20 0. 019 O. 014 0. 52 27. 26 0120 0. 23 D 6. 09 0. 009' 0. 008 0. 30 24. 80 0. 13 0. 24' E. 5. 96 0.004 0. 008 0. 38 21. 07 2. 58 0. 23 F 5. 67 0. 005 0. 007 0. 35 20. 42 5. 0. 22 G 5. 92 0. 009 0. 009 0. 33 21. 12 0. 14 0. 11 II 6. 06 0. 009 O. 006 0.32 21. 13 0. 13 0. 17 I 6. 04 0. 000 O. 012 0. 27 21.12 0. 21 0. 23 J 6.05 0. 009 0. 012 0. 26 21. 16 0.21 0. 24 K 5. 89 0. 008 0. 000 0. 41 22. 48 0. 74 0. 26 L 5. 76 0. 000 0. 006 0. 38 24. 1. 22 0. 25 M 5. 96 0. 003 0. 007 O. 33 15. 28 0. 18 0. 22 N. 5. 82 0. 004 0. 007 0. 33 17. 75 0. 18 0. 26 O 3. 36 0. 006 0. 007 0. 42 20. 57 0. 0. 22 P-.. '8. 77 0. 009 0. 008 0. 40 20. 93 0. 20 0. Q, 5. 74 0. 007 0. 008 0. 32 20. 99 0. 19 0. 25

Table II below summarizes the effect of the austenite percentage level on the hardness and toughness of the heats of Table I both in the annealed and austenitized condition. In Table II the heats are listed in the order of increasing austenite content. Heats L, I, B, J and K fall within the preferred austenite levels of 20 percent to percent, and heats I and B have optimum properties. i

TABLE I1 Ann.=Annealed 788 C.-4 hrs.-A.C.

The austenite percentage was measured on a calibrated permanent magnet gauge known as a MAGNE- GAGE.

The data of Table II. indicate that for nitrogen contents over about 0.20 percent, an average of at least 20 percent austenite is needed to impart good toughness. With nitrogen contents less than about 0.20 percent, a minimum average austenite level of 10 percent is sufficient to impart satisfactory toughness.

Tables III through VIII below list certain selected heats and compare the effect on hardness and toughness of variation of chromium, manganese, nitrogen, carbon, nickel, and chromium plus nickel, respectively, all other elements in each Table being substantially constant.

The data on hardness are included to show transformation to martensite. High hardness indicates that transformation to martensite has occurred. The magnetism values measure both ferrite and martensite since both are magnetic, but if the hardness does not increase after annealing or austenitizing, substantially all the magnetic phase remains as ferrite.

' TABLE III Effect of Chromium Content on Properties 1 Much of the austenite in these heats transformed to martensite.

TABLE IV Effect of Manganese Content on Properties (Heats are listed in order of increasing manganese) CVN Impact strength, Percent Hardness kgmJe'm. austenite measured Heat 0. Mn Ann Aus. Ann Aus. Ann. Aus. Avg.

() 3.4 1390 B04 0.8 8.3 7 30 18 B 5. 8 B92 B94 8. 6 16. 5+ 25 25 25 I 6. 0 B95 B95 5. 4 16. 5+ 21 20 20 P 8. B97 B95 16. 5+ 16. 5+ 38 32 35 I Some of the austenite in this heat appears to have transformed to ferrite.

Aus.=Austenltlzed 1,038 C.-15 mins.-W.Q.

Efieet of Austenite 0n Properties CVN im act Rockwell strengt Percent austenite hardness kgmJem. measured Heat No C Mn Cr N Ann. Aus. Ann. Aus. Ann. Aus. Avg.

A 0. 12 0. 26 0. 20 0. 4 0. 6 2 2 2 G 5 5.9 21.1 0.11 1386 B91 1.0 3.2 6 6 6 D 6. 1 24. 8 0. 24 B91 B95 0. 6 2. 2. 4 l0 7 C 6. 2 27. 3 0. 20 B93 B92 0. 6 0. 4 i! 1) 9 H 6.1 21. 1 0.17 B B92 2. 6 6. 4 12 0 ll M 6. 0 15. 3 1 0. 22 C42 C44 1.1 2. 8 R 20 14 O 3. 4 20. 6 Z 0. 22 B00 B94 0. 8 B. 8 7 30 IR 5. 8 24. l 0. 25 B94 B06 2. 2 l1. 2 1!; 2] 20 6. O 21. 1 0. 23 I305 I305 5. 4 16. 5+ 21 20 20 5. 8 21. l 0. 23 B92 B 8. 6 16. 5+ 25 25 5 6. 0 2i. 2 0. 24 B95 B05 5. 3 16. 5+ 26 21 25 5. 9 22. 5 0. 26 B95 B96 4. 3 16. 5+ 24 32 2X 5. 8 I7. 8 l 0. 26 C31 C30 0.4 l. 8 34 32 33 8. 8 20. 9 0. 25 B07 B95 16. 5+ 16. 5+ 38 32 35 5. 7 2]. 0 0. 25 B96 B05 5. 16. 5+ 37 35 36 6. 0 21. 1 0. 23 B B96 16. 5+ 16. 5+ 65 58 61 5. 7 20. 4 0. 22 B95 B92 16. 5+ 16. 5+ 92 89 '90 l Low'chromium austenite transformed to martensite.

1 Low manganese austenite transformed to ferrite.

A Charpy V notch impact strength of 2 kgm/cm in the annealed condition is considered the minimum acceptable toughness.

From Table III it will be noted that with all other elements substantially constant, chromium contents of less than about l9 percent permit the austenite to TABLE V Effect of Nitrogen 'fthe range of 0.013 percent to 0.055 percent increase Content on Properties (Heats are listed in order otinereasing mtrogen) the austen te content but have little effect on tough- CVN impact 'ness? strength, Percent H6 t H dn em-le austenite measured 5 Table VII shows the effect of nickel in control of the a Nd. N Arm. Ans. Ann. Aus. Ann. Aus'. Avg. austenlte-ferrlte balance. With all other elements subg g 3 1'0 6 6 stantially constlant, nickel contents i; the range of 0.14

.1 o 92 2.6 6.4 12 9 11 Ce t c t r M3 B95 B95 5.4 m5+ 21 20 20 per 11 to 5 per en inc ease t e austenite lrom 0.2a B92 B94- s.s 16. 5+ 25 25 25 about 20 percent to about 90 percent with good tough- I ness over the entire range. TABLE VI Etfiect e (ialzgon (ipntepit 011 g r o ertieg The effect on toughness of varying the chromium and 8 I] ea Sat 8 e or em more ng cat on) nlckel contents while maintaining a constant austenite ("lftglirgntgaet Percent level is shownin Table Vlll. With all other elements He t Hardness t' -lc austenite measured substantially constant, a chromium content of just over a Ann Arm Aug AmL Aus, Avg 1 24 percent with 1.2 percent nlckel cause a significant B95 B95 4 16I+ 21 2o decrease in toughness. B92 B95 8.6 16.5;1- 25 25 25 gas 1 395 5.3 16. 5+ 26 24 25 Mechamcal propertles of the steels of the rnventio 96 96 165+ 37 36 are set forth in Table IX below.

. TABLE IX Annealed Austenltlzed Percent CVN Percent CVN 0.2% elong. Percent impact 0. clong. Percent impact U.'I.S., Y.S., in red. Rockwell strength, U.T.S., Y.S., in red. Rockwell strength, MN/mfl MN/nifi 5cm. area hardness kgmJcm. MN/m.' MN/m. 50111. area hardness kg111./cn1.'- 735 516 40 50 1392 8.6 682 434 40 65 B95 16.5+ 750 430 48 69 B100 16. 5+ 746 465 44 71 B96 16. 5+ 710 434 39 51 B90 2.6 646 434 as on n92 6.4 756 468 as 40 B95 5.4 695 441 3 e7 1395 1e.5+ 1395 5.3 710 454 40 as B95 16. 5+ 744 51a 31 57 B95 4.3 710 480 36 08 B96 16. 5+ 724 432 32 56 B94 2.2 724 530 36 65 B96 11.2 764 454 47 65 1397 1115+ 703 441 74 B05 16. 5+ 860 427 40 44 B96 5.4 710 441 45 on 1395 16.5-1-

TABLE v11 Efiecwfmckel Content onPmpemes Weld area corrosion tests were conducted on sam (Heats are listed in order ollncreaslng nickel) ples of Heat B, a preferred composition of the inven- CVN impact 35 tion, with the following results:

strength, Percent H t Hardness kgmJcmfl' austenite measured Cuso4 65% Boiling Boning Mgcll U A393 HNO, 1240 Hours 0 1 Ann An Ann Ans Ann Aus Avg Ann. Aug. Ann. Ans. Ann. Aus. B92 B94 8.6 16. 5+ 25 25 25 No corro No corro- .00201PM .00141PM No No B95 B95 21 0 30 sion sion No accel. No. accel Cracks Cracks a a; 122 122 24 a 2:, 5 The boiling HNO tests comprised 3 48-hour periods. TABLE VH1 From the above data it is apparent that there is pro- Efiect ol Chromium and Nickelpcontint with Constant Austcnite on vlded a stamless steel which, by reason of its composi- (Heats are listed in 3,;?f, Cr and Ni) tion and critical balance of essential elements, achieves CVNimpact 45 the objectives hereinbefore stated.

trength, Ifereeut The embodiments of the invention in which an excluf i ji i u 12 33 193 3 0??? sive property or privilege is claimed are defined as fol- Ni Ann. Aus. Ann. Ans. Ann Aus. Avg. l 0.14 1392 B94 2.5 16. 5+ 25 25 25 1. A stainless steel having a two-phase structure com- I 81;; 32 32 21% {2;21 3 prising between 10 percent and 50 percent austenite 1n B94 B95 19 a ferrite matrix, consisting essentially of up to about transform to martensite. thereby increasing the hardness and reducing the impact strength. Chromium contents greater than about 24 percent decrease the quantity of austenite and the impact toughness.

Table IV indicates that with all other elements substantially constant manganese contents of less than about 4 percent result in a transformation of austenite to ferrite.

Table V shows the effect of nitrogen in control of the austenite-ferrite balance. Nitrogen contents of less than about 0.12 percent, with all other elements substantially constant, result in too low an austenite content to provide good toughness.

The effect of carbon in control of the austeniteferrite balance is shown in Table VI. With all other elements substantially constant, carbon contents within 0.06 percent carbon, about 4.0 percent to less than 11.0 percent manganese, about 19 percent to about 24 percent chromium, about 0.12 percent to about 0.26 percent nitrogen, nickel up to about 3.0 percent, phosphorus and sulfur up to about 0.03 percent each, silicon up to about 1.0 percent, copper and cobalt up to about 0.5 percent each, and remainder substantially lIOll.

' 2. The stainless steel of claim 1, containing about 0.02 percent carbon, about 6.0 percent manganese, about 21.0 percent chromium, about 0.20 percent nitrogen, about 0.20 percent nickel, and about 0.40 per cent silicon.

3. The stainless steel of claim 1, wherein carbon is present in an amount of about 0.02 percent.

4. The stainless steel Jf claim 1, wherein manganese is present in the amount of about 6.0 percent.

5. The stainless steel of claim 1, wherein chromium is present in the amount of about 21.0 percent.

6. The stainless'steel of claim 1, wherein nitrogen is present in the amount of about 0.20 percent. v 7. The stainless steel of claim 1, wherein nickel is present in the amount of about 0.20 percent.

8. The stainless steel of claim 1, wherein molybdenum is substituted for chromium on a lzl basis in amounts up to about percent.

9. The stainless steel of claim 1, including columbium in amounts up to about 1 percent.

10. A stainless steel having a two-phase structure comprising between 20 percent and 30 percent austenite in a ferrite matrix, consisting essentially of about 0.02 percent carbon, about 6.0 percent manganese, about 21.0 percent chromium, about 0.20 percent nitrogen, about 0.20 percent nickel, phosphorus and sulfur low, about 0.40 percent silicon, copper and cobalt low, and balance substantially iron.

11. Welded articles having a. two-phase structure comprising between percent and 50 percent austen ite in a ferrite matrix, consisting essentially of up to about 0.06 percent carbon, about 4.0 percent to less than 11.0 percent manganese, about 19 percent to about 24 percent chromium, about 0.12 percent to about 0.26 percent nitrogen, nickel up to about 3.0 percent, phosphorus and sulfur up to about 0.03 percent each, silicon up to about 1.0 percent, copper and cobalt up to about 0.5 percent each, and remainder substantially iron. 

2. The stainless steel of claim 1, containing about 0.02 percent carbon, about 6.0 percent manganese, about 21.0 percent chromium, about 0.20 percent nitrogen, about 0.20 percent nickel, and about 0.40 percent silicon.
 3. The stainless steel of claim 1, wherein carbon is present in an amount of about 0.02 percent.
 4. The stainless steel of claim 1, wherein manganese is present in the amount of about 6.0 percent.
 5. The stainless steel of claim 1, wherein chromium is present in the amount of about 21.0 percent.
 6. The stainless steel of claim 1, wherein nitrogen is present in the amount of about 0.20 percent.
 7. The stainless steel of claim 1, wherein nickel is present in the amount of about 0.20 percent.
 8. The stainless steel of claim 1, wherein molybdenum is substituted for chromium on a 1:1 basis in amounts up to about 5 percent.
 9. The stainless steel of claim 1, including columbium in amounts up to about 1 percent.
 10. A stainless steel having a two-phase structure comprising between 20 percent and 30 percent austenite in a ferrite matrix, consisting essentially of about 0.02 percent carbon, about 6.0 percent manganese, about 21.0 percent chromium, about 0.20 percent nitrogen, about 0.20 percent nickel, phosphorus and sulfur low, about 0.40 percent silicon, copper and cobalt low, and balance substantially iron.
 11. Welded articles having a two-phase structure comprising between 10 percent and 50 percent austenite in a ferrite matrix, consisting essentially of up to about 0.06 percent carbon, about 4.0 percent to less than 11.0 percent manganese, about 19 percent to about 24 perCent chromium, about 0.12 percent to about 0.26 percent nitrogen, nickel up to about 3.0 percent, phosphorus and sulfur up to about 0.03 percent each, silicon up to about 1.0 percent, copper and cobalt up to about 0.5 percent each, and remainder substantially iron.
 12. Cold headed fasteners having a two-phase structure comprising between 10 percent and 50 percent austenite in a ferrite matrix, consisting essentially of up to about 0.06 percent carbon, about 4.0 percent to less than 11.0 percent manganese, about 19 percent to about 24 percent chromium, about 0.12 percent to about 0.26 percent nitrogen, nickel up to about 3.0 percent, phosphorus and sulfur up to about 0.03 percent each, silicon up to about 1.0 percent, copper and cobalt up to about 0.5 percent each, and remainder substantially iron. 